Minerals Engineering 209 (2024) 108637

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Minerals Engineering
journal homepage: www.elsevier.com/locate/mineng

Residual Dewatering Aids in Process Water on Flotation Performance of a

Selected Cu-Ni-PGM Ore from a Siliceous Reef
Malibongwe S. Manono *, Saahil F. Khan , Lisa L. October , Kirsten C. Corin
Centre for Minerals Research, Department of Chemical Engineering, University of Cape Town, Private Bag X3, Rondebosch 7701, South Africa

A R T I C L E I N F O A B S T R A C T

Keywords: The increasing scarcity of water has led to mine operations recycling water from tailing dams, thickener over­
Coagulants, Depressants flow, dewatering and filter products. However, water quality is found to influence the process of ore flotation,
Dewatering Agents with adverse effects on flotation selectivity. The adsorption of the collector onto valuable minerals may also be
Flocculants
affected by the unintended change on water chemistry. This study simulates the impact of dewatering reagents
Flotation Reagents
Process Water
present in recycled water from tailings dewatering unit operations into the flotation process using a Silicate reef
ore from the South African Bushveld Igneous Complex (BIC) supplied by Pilanesburg Platinum Mines. Unique
plant water (UPW), consisting of inorganic electrolytes and dewatering chemical reagents, was synthetically
prepared using water quality analyses received from a South African concentrator processing a Cu-Ni-PGM
bearing Merensky ore. The study has a specific focus on the impact of flocculants and coagulants as dewater­
ing reagents present in recycled process water on solids recovery, water recovery, copper and nickel mineral
recovery, copper and nickel mineral grade, residual concentrations of the collector post flotation are also
determined as well as particle settling of the tails after flotation. The results show that the presence of dewatering
reagents in recycled process water into the flotation system may result increased mineral particle recoveries, both
the valuable minerals and gangue. However, the increase in gangue recoveries may be to the detriment of the
concentrate grades with respective to the valuable minerals of interest. The ability to pull more solids to the
concentrate could further have considerable implications on the dewatering of tailings post flotation as each
condition resulted in distinct tailings settling tendency. It was also shown that there was little to no influence on
the adsorption of the freshly dosed collector as its residual concentrations in the tails remained fairly the same
across the tested process water conditions containing residual concentrations of the coagulant, depressant and
flocculant.

1. Introduction
Flotation is a mineral processing technique used to separate valuable
minerals from unwanted material (Fuerstenau et al., 2007; Wills and
Napier-Munn, 2006). This study focused on the Merensky reef, found in
the South African Bushveld Igneous Complex, which is home to the
largest deposits of Platinum Group Minerals (PGMs) in the world. As
water scarcity becomes an increasing concern, recycling water within
mining operations becomes essential to lower water demand and
potentially hazardous environmental discharge, as well as reagent
consumption thus lowering operating costs to some extent. However, the
quality of recycled water has been found to have an adverse effect on
flotation selectivity (Bicak et al., 2018; Biçak et al., 2012; Muzenda,
2010; Levay et al., 2001; Manono et al., 2018a; Michaux et al., 2018;
Öztürk et al., 2018; Schumann et al., 2003; Sinche-Gonzalez et al., 2016;
Sinche-Gonzalez and Fornasiero, 2021; Slatter et al., 2009). This study
aims to determine the influence of residual dewatering reagents in
recycled process water on the overall flotation process. The primary
focus is on flocculants and coagulants which are often added into
thickeners to aid the sedimentation of concentrate and tailings and
clarification of water that is recovered and returned to the process for
milling and flotation purposes. As little research has been done on this
topic, this study is necessary to determine if there are any detrimental or
beneficial effects that residual concentrations of these dewatering aids
would have on flotation performance.
The process of dewatering flotation products – slurries post-flotaion

* Corresponding author.
E-mail addresses: malibongwe.manono@uct.ac.za (M.S. Manono), KHNSAA001@myuct.ac.za (S.F. Khan), lisa.october@uct.ac.za (L.L. October), kirsten.corin@
uct.ac.za (K.C. Corin).

https://doi.org/10.1016/j.mineng.2024.108637
Received 21 September 2023; Received in revised form 7 February 2024; Accepted 21 February 2024
Available online 1 March 2024
0892-6875/© 2024 The Author(s). Published by Elsevier Ltd. This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-
nc-nd/4.0/).
M.S. Manono et al.
involves the separation of the final concentrate or tailings from a pulp
with a high water-solids ratio. While there are multiple methods for
dewatering of flotation products, about 80 % of the water can be
recovered through sedimentation. Sedimentation is the process of
rapidly settling solid particles to produce a clarified liquid that can be
decanted, leaving behind a thickened slurry (Sharma et al., 2006). It is
most efficient when there is a large density difference between the liquid
and the solid particles. Particles that are only a few microns in diameter
can take extremely long to settle by gravity alone, to tackle this problem
the coagulation and flocculation processes can be used sometimes with
the aid of dewatering chemical reagents (Napier-Munn and Wills, 2005).
Coagulation and flocculation processes can be used to improve the ef­
ficiency of sedimentation. Dewatering aids are used for purposes of
improving the coagulation-flocculation-sedimentation of slurries. The
coagulation process causes extremely fine colloidal particles to adhere
directly to each other. All particles exert mutual attraction forces known
as Van der Waals forces. In normal circumstances adhesion due to these
forces is prevented by the electrically charged region around each par­
ticle which generates repulsive forces between particles approaching
each other. This results in a balance in any given system between the
attractive and repulsive forces present at the solid–liquid interface
(Napier-Munn and Wills, 2005; Bratby, 2016). Dewatering aids known
as coagulants are used to overcome these repulsive forces which would
then cause the fine particles to adhere to each other. Coagulants are
electrolytes that overcome the repulsive forces between particles, while
flocculants aggregate dispersed particles to form large particle aggre­
gates that settle more easily. Inorganic salts have long been used for this
purpose and as counter ions in aqueous systems are commonly positively
charged. Salts containing highly charged cations such as Al3+ and Fe3+
are mainly used (Bratby, 2016; Napier-Munn and Wills, 2005).
Flocculation is a process whereby finely dispersed particles are
aggregated together to form large particles which can then settle and
cause the clarification of the system. Flocculants are the reagents which
are used in this process to decrease the repulsive forces and increase the
attractive forces (Sharma et al., 2006). There are two mechanisms by
which flocculation occurs, namely, the polymer bridging theory and the
patch model. In the polymer bridging theory, the destabilization of the
particle occurs when the polymer chain adsorbs on more than one
particle, this results in the linking of multiple particles together. This
further results in the formation of a particle-polymer-particle aggregate,
thereby enhancing the flocculation of solids. The patch model or the
electrostatic mechanism involves the use of uneven distribution of
charges resulting from the adsorption of discrete patches of polymers on
the surface. Highly cationic polymers are adsorbed onto a negative
particle surface, this adsorption promotes flocculation by reducing the
overall negative charge which reduces the inter repulsive forces, this is
referred to as charge neutralization. In addition to charge neutralisation,
positive regions of the polymer are attracted to negative regions on other
particles, this is referred to as heterocoagulation (Sharma et al., 2006).
There are two major categories of flocculants; these are organic and
inorganic flocculants. Inorganic flocculants have been used for an
extremely long time and consist of salts of multivalent metals such as
aluminium and iron. However, there are several disadvantages in using
them; they are consumed in large quantities and produce large amount
of sludge, are highly sensitive to pH, work on a limited number of sys­
tems, and do not work on very fine particles. These reasons have led to
these flocculants being less preferred compared to organic flocculants
(Sharma et al., 2006). The organic flocculant category can be further
divided into natural bioflocculants and grafted flocculants. It is the
polymeric flocculants under these categories that have become vastly
popular due to their natural inertness to pH changes, high efficiency
with low dosage and easy handling (Lee et al., 2014). However, they
have their disadvantages related to their degradability and environ­
mental impact (Lee et al., 2014). The polyacrylamides (PAM) are the
most common flocculants, these can be manufactured to have non-ionic,
anionic, and cationic character.
2
Minerals Engineering 209 (2024) 108637
Organic flocculants are becoming more popular due to their higher
efficiency and lower dosage requirements, although they have some
environmental drawbacks (Bulatovic, 2007; Sharma et al., 2006).
The use of flocculants and coagulants in the dewatering or thickening
process is known to be sensitive to particle size (Sharma et al., 2006). It
is, however, unclear whether fine particles in flotation subjected to
process water containing residual concentrations of these dewatering
agents would be impacted through the formation of larger particle ag­
gregates, which in turn may affect key sub-processes of flotation such as
bubble-particle attachment since particle size is key to flotation per­
formance. The effect of particle size on flotation has been extensively
researched, with both fine and coarse particles known to negatively
impact the performance of the process (Aktas et al., 2008; Chidzanira,
2016; Collins and Jameson, 1976; Dobby and Finch, 1987; Feng and
Aldrich, 1999; Gaudin et al., 1942; Hassanzadeh et al., 2019, 2018,
2016; Hu et al., 2003; Johansson and Pugh, 1992; Leistner et al., 2017;
Pérez-Garibay et al., 2014; Sajjad and Otsuki, 2022; Senior et al., 1995;
Trahar, 1981; Zhang et al., 2017). It is therefore crucial to operate at the
optimal grind size. Fine particles, defined as those less than 10 μm, result
in slower recovery rates due to reduced bubble-particle collision,
excessive adsorption of reagents and increased entrainment, leading to
poor results in grades and recoveries (Ahmadi et al., 2014; Farrokhpay
et al., 2020; Feng and Aldrich, 1999; Forbes, 2011; Sajjad and Otsuki,
2022; Senior et al., 1995; Tao et al., 2000; Trahar, 1981; Wang, 2016;
Yoon and Luttrell, 1989; Zhang et al., 2017). Conversely, coarse parti­
cles, larger than 70 μm, disrupt bubble-particle aggregation in turbulent
zones and have reduced buoyancy relative to the pulp, resulting in
decreased recovery rates (Bournival et al., 2014; Farrokhpay and For­
nasiero, 2017; Ni et al., 2023; Wang et al., 2014; Wang and Peng, 2014).
Moreover, coarse particles require a higher degree of hydrophobicity for
better floatability (Feng and Aldrich, 1999; Senior et al., 1995; Trahar,
1981; Zhang et al., 2017). Intermediate particles, between 10 and 70
μm, provide the best flotation results as they are well liberated and float
at a rate that provides optimum recovery through true flotation,
providing the best selectivity. Overall, particle-bubble interaction is a
key factor in the flotation process, highlighting the importance of par­
ticle size optimization for efficient and effective flotation (Feng and
Aldrich, 1999; Senior et al., 1995; Trahar, 1981; Zhang et al., 2017).
Therefore, it stands to reason that residual dewatering reagents in
recycled process water are important to consider as they may change the
particle size or compete with flotation reagents for adsorption onto
mineral particles.
Studies have been conducted on the effects of ions in process water
on flotation performance due to the increased recycling of water in the
mining industry. It has been shown that water quality plays a crucial role
in flotation, and the influence of ions and their concentration was found
to affect froth stability of the through the formation of smaller and more
stable bubbles resulting in higher water and solids recoveries (Bicak
et al., 2018; Biçak et al., 2012; Corin et al., 2011; Corin and Wiese, 2014;
Farrokhpay and Zanin, 2012; Levay et al., 2001; Manono et al., 2012;
Schumann et al., 2003; Sinche-Gonzalez and Fornasiero, 2021).
Increasing the ionic strength of the water used in sulfide mineral flota­
tion was found to increase solids and water recoveries, while the sulfide
grade decreased as ionic strength of the water increased. This was
attributed to the stabilisation and mobilisation of the froth with
increased water recovery and the fast-floating nature of the valuable
minerals as well as an increase in the recovery of gangue through
entrainment. It is worth mentioning that organics in process water have
also been shown to impact the flotation of sulfide minerals, however
there is limited research on the impact of residual organics in process
water on flotation performance (Sinche-Gonzalez et al., 2016). As little
or no research has been done on the influence of residual dewatering
aids present in process water on flotation performance, this study con­
siders the presence of a coagulant, flocculant and a flotation depressant
in process water on the flotation performance of a Cu-Ni-PGM ore from
the Merensky reef in order to mimic the influence of recycled water with
M.S. Manono et al. Minerals Engineering 209 (2024) 108637

residual polymer concentrations. Table 2

Mineralogy of the ore in wt.%, adapted from Becker et al. (2014).
2. Materials and methods Minerals Composition, wt %

Base metal sulfides 0.2

2.1. Unique plant Water (UPW) preparation Olivine 3.8
Orthopyroxene 24.6
In order to best mimic the process water on site received from a Clinopyroxene 10.3
Serpentine 10.6
South African PGM concentrator, a unique synthetic plant water recipe
Talc 18.0
was developed using the methodology described by Smith et al. (2002). Chlorite 5.1
This method considers each inorganic ion in a specific sequence to Amphibole 6.8
ensure the correct concentrations for each component are achieved. The Epidote 1.2
resulting plant water was termed unique plant water (UPW) and the K-feldspar 0.1
Mica 0.9
inorganic electrolyte concentration can be seen in Table 1. Salts of
Calcite 1.0
analytical grade, supplied by Merck, were dissolved in de-ionised water Quartz 0.3
to prepare this UPW with the quality shown in Table 1. Chromite 0.8
Iron oxides 11.0
Other 0.9
2.2. Ore Preparation and mineralogy

A bulk sample of a ‘‘silicate reef’’ ore was received from Pilanesburg

Platinum Mines in South Africa. The ore sample had a top size of 80 mm Table 3
Reagents used for Milling and Flotation.
when it was received by the Centre for Minerals Research (CMR) at the
University of Cape Town (UCT) for experimental tests. The bulk sample Reagent Name Main Component Dosage Purpose Onsite
was crushed to a top-size of − 1 mm, blended, riffled and split into 1 kg Gemcol SIBX (Sodium Isobutyl Xanthate) 143 g/t Collector
samples using a rotary splitter prior to batch flotation tests. The split Flomin F200 Alcohol and ether 40 g/t Frother
samples of 1 kg were stored in zip sealed air -tight bags. The mineralogy
of the selected ore is shown in Table 2. Prior to batch flotation tests, the
Sodium isobutyl xanthate (SIBX) in the form of Gemcol, as the collector,
1 kg samples were milled to 80 % passing 75 μm in a stainless-steel
was added to the mill at a fixed dosage of 143 g/t for all tests. Flomin
laboratory rod mill at 66 % solids density with unique plant water
F200 was added to the batch flotation cell as a frother at a dosage of 40
(UPW).
g/t.
It can be seen from the bulk mineralogical analysis of ore shown in
Table 4 shows the coagulant, depressant and flocculant obtained
Table 2 that the PPM ore from the “silicate reef” was dominantly
from the mine. The coagulant and flocculant are dewatering aids which
comprised of orthopyroxene (24.6 wt%), clinopyroxene (10.3 wt%), the
the mine site adds to their thickeners for tailings dewatering purposes;
alteration minerals (10.6 wt% serpentine, 18.0 wt% talc, 5.1 wt%
residual concentrations of these are seen in the return water from the
chlorite, 6.8 wt% amphibole) and the iron oxides (11.0 wt%). The base
tailings thickener overflow. The depressant is used to selectively depress
metal sulfides (BMS) content of the ore was only 0.2 wt%. The signifi­
non-sulfide naturally floatable gangue but exists in the tailings water in
cant enrichment of the alteration minerals and iron oxides as well as the
residual amounts or concentrations. It must be highlighted that
low base metal sulfides (BMS) composition are characteristic of altered
WM7530 and WM8305 are both used for dewatering purposes whilst
and oxidised PGM ores (Oberthür et al., 2013) because other ores from
(FinnFix300) is used onsite as a depressant and usually has considerable
the Bushveld Igneous Complex (BIC) such as the Merensky reef often
residual concentrations in the return water from tailings thickeners. WM
contain a total BMS composition in the 1 wt% range (Becker et al., 2009;
7530 is an acrylamide-acrylate co-polymer, anionic in nature and is used
Corin et al., 2011). Becker et al. (2014) also noted that the plagioclase
as a flocculant, whilst WM 8305 is a poly hydroxyalkylene dimethyl
content of this ore was rather low (4.4 wt%) compared to other Mer­
ammonium chloride, cationic in nature and is used as the coagulant in
ensky ores, citing mineralogical analyses published in Solomon et al.
tailings thickeners. FinnFix300 is a carboxymethyl cellulose (CMC),
(2011) and in Vogeli et al. (2011). They attributed this to the mining cut
which is used as a gangue depressant for flotation of the selected ore.
and the processing of ‘‘silicate reef’’ compared to pure Merensky reef
The necessary residual reagents, depressant (D), flocculant (F), and
rather than the effect of any oxidation that may have occurred on the
coagulant (C) shown in Table 4 were added to the volume of the syn­
stockpile from which the ore was received.
thetically prepared UPW required in the mill to ensure a 66 % solids
density of the milled slurry. These were added according to the dosages
2.3. Reagents shown in Table 5 in order to simulate recirculated process water con­
taining residual concentrations of the depressants and dewatering aids.
Table 3 shows the reagents that were used for flotation which were In Table 5, the concentration of residual reagents in process water are
dosed as supplied. These reagents were provided by the mine site. The presented in mg/L and these dosages were based on onsite water quality
reagents were dosed as supplied and not corrected for active content. data provided by the mine site processing the selected ore. The baseline
condition is denoted by None (N), i.e., no residual reagent in the process
Table 1 water.
Concentration of ions in UPW.
Ions Concentrations mg/L

Ca 2+
17.32 Table 4
Cl- 184.60 Reagents used as Residual Reagents in Process Water.
Mg2+ 12.03
Reagent Main Component Purpose
K+ 12.68
Name Onsite
Na+ 216.89
H+ 2.38 FinnFix300 Carboxymethyl Cellulose (CMC) Depressant
CO2–3 142.98 WM 7530 Acrylamide-acrylate co-polymer Flocculant
SO2-4 193.34 WM 8305 Poly hydroxyalkylene dimethyl ammonium Coagulant
TDS 782.22 chloride

3
M.S. Manono et al. Minerals Engineering 209 (2024) 108637

Table 5 2.6. Adsorption studies on tailings filtrate for residual reagent

Experimental Conditions for the Residual Reagents Tested. concentration of SIBX after flotation
Experimental Factors and Levels for Each Factor
Condition Name Because the adsorption of SIBX onto Cu-Ni sulfide minerals is critical
Coagulant Flocculant Depressant
(WM8305) dosage (WM7530) dosage (CMC) dosage to flotation performance, the influence of dewatering aids in process
(mg/L) (mg/L) (mg/L) water on the residual concentrations of SIBX in water recovered from
None – – –
tailings post-flotation was determined as this would allow to determine
D – – 60 whether the residual dewatering had any effect on the adsorption of the
C 15 – – collector onto valuable sulfide minerals, therefore residual concentra­
F – 4 – tions of SIBX in tailings recovered water was more of importance other
than residual concentrations of the coagulant, flocculant and depressant
which were already dosed as residual chemicals in the feed water to
2.4. Flotation
milling and flotation. Residual collector analyses were therefore con­
ducted on the tailings filtrates. Two tailings filtrate samples from each
Flotation reagents were measured by mass rather than volume, and a
test were analysed for residual residual SIBX concentration. The UV–Vis
measuring cylinder was washed three times with synthetically prepare
spectrophotometer (Biochrom, Holliston, MA, USA) was used to deter­
unique plant water (UPW) to ensure accurate delivery. Collection trays,
mine the concentration of SIBX collector in the tailings filtrate samples.
wash bottles, top-up water bottles, and filter papers were weighed prior
The absorbance peak of SIBX was found to be at 301 nm as established in
to use. Following ore preparation, the slurry was transferred to a 3 L
the literature (October et al., 2019, 2020). The tailings filtrate samples
Barker batch flotation cell. The flotation process was then conducted
were further filtered through a 0.45 µm syringe filter before being placed
using the standard UCT batch flotation procedure as outlined in Table 6,
in quartz cuvettes for analyses. The Beer-Lambert law was applied to
adapted from Wiese et al. (2005).
calculate absorbance, a standard calibration curve was developed before
After completing the flotation process, three tailings samples were
testing the flotation samples such that the unknown SIBX concentration
taken using 10 mL syringes. All the trays and water bottles used during
in the tailings filtrate samples was determined using the measured
the process were weighed. The final step involved filtering the concen­
absorbance. This method accurately measures the concentration of SIBX
trate samples through a Buchner funnel. The filtered solids concentrate
in solution samples, particularly those of water meant to be recycled for
was collected on filter paper and dried in an oven at 80 ◦ C overnight,
milling and flotation purposes. Experiments were repeated, thus
while the filtrates were stored in sample jars at room temperature for
ensuring that a standard error was calculated as shown in the error bars
further testing. The two feed and two tailings samples were filtered,
in Fig. 10.
dried and weighed. XRF analyses of all solids for Cu and Ni were con­
ducted using an Olympus Vanta from InnoX Africa. In order to minimise
error and ensure reproducibility of the results, all tests were performed 3. Results and discussion
in duplicates (see error bars in Figs. 2–8).
3.1. Solid and water recoveries
2.5. Tailings settling tests
Fig. 1 shows the final solids and water recoveries achieved under the
different conditions tested in this study.
In order to study the influence of having residual concentrations of a
It is evident form Fig. 1 that the total cumulative water and solids
coagulant, depressant and flocculant in process on the dewatering of
recoveries increased in the order F > C > D > N, i.e. higher water and
flotation tailings, settling tests were conducted on the third tailings
solids were achieved in process water containing a flocculant, followed
sample after flotation. The particle settling rate measurements were
by process water containing a coagulant, this too was followed by pro­
conducted by taking 10 mL tails sample. The sample was transferred to a
cess water containing residual concentrations of the depressant, with the
sample vial and shaken for 30 sec before being placed in a Hannah
lowest solids and water recoveries obtained in process water containing
turbidity meter. A stopwatch was immediately started, and turbidity
none of the dewatering aids and depressant. The results of this work
readings were taken at 90 sec intervals for 1 hr. This method was
have shown that the addition of the selected dewatering aids increased
developed and adapted from studies considering the effects of co­
mass pull. These results are further illuminated in Fig. 2 and Fig. 3 where
agulants and flocculants on particle settling (Sharma et al., 2006).
solids and water recoveries are presented as functions of time,
Settling tests were conducted on all samples obtained from the duplicate
respectively.
flotation runs so as to ensure reproducibility and minimum experimental
Fig. 2 shows that majority of the solids are recovered in the first 2
error (see error bars in Fig. 9).
min of the process for the UPW containing residual concentrations of the
coagulant (C) and flocculant (F). The highest solids recoveries per min
Table 6
were achieved under the condition with the flocculant (F) in the system.
UCT Batch Flotation Procedure.
While the lowest solids recoveries per min were obtained in the absence
Time Step of all three polymers (None). This therefore implies that the rate of re­
(min)
covery of solids was in the order of F > D > C > N, thus showing that
Prestart Impeller speed set at 1200 rpm mass pull rates were higher in process water containing residual con­
00:00 Start the stopwatch
centrations of the flocculant, depressant and coagulant compared to the
01:00 Take 2 feed samples using 10 mL syringes for analysis of solids and
residual reagent analysis of water baseline condition without any of the residual polymers.
02:00 Dose Frother 40 µL using a micro syringe and condition for 1 min Fig. 3 shows that the rate of water recovery is highest in the first 8
03:00 Open feed air valve, ensure air flowrate is maintained at 7 L/min min of flotation after which the rate slows down significantly. The
From this point, the scraping/ collecting process is carried out every 15 presence of residual reagents resulted in distinct water recovery rates
sec
05:00 The first sample collection tray is removed (2 min flotation)
that were higher compared to the rate of water recovery for the baseline
09:00 The second sample collection tray is removed (4 min flotation) condition (N). The rate of water recovery increased in the order F > C >
15:00 The third sample collection tray is removed (6 min flotation) D > N. The residual concentrations of dewatering aids in process water
23:00 The fourth sample collection tray is removed (8 min flotation). The feed consistently showed increased solids and water recoveries compared to
air is turned off
the baseline condition as well as the condition containing residual
Adapted from Wiese et al. (2005) concentrations of the depressant in process water as shown in both Fig. 2

4
M.S. Manono et al.
Fig. 1. Final Solid and Water Recoveries in Unique Plant Water with Residual Dewatering Reagents.
Fig. 2. The Relationship between Solids Recoveries and Flotation Time in Unique Plant Water with Residual Dewatering Reagents.
and Fig. 3.
The increase in solids and water recovery in the presence of residual
amounts of dewatering agents is attributed to the ionic properties of the
reagents that were added to the system which would have resulted in an
increase in the total ionic strength of the process water. An increase in
ionic concentration of process water is known to increase the stability of
the froth, which results in an increase of solids and water recoveries
(Corin et al., 2011). This has been shown in previous studies where for
example the addition of a pH modifier, meant to increase the pH from
pH 9 to pH 11, not only increased the pH, but aided in higher water
recoveries and was attributed to the addition of ions such as Ca2+ which
are known to result in smaller bubbles, thus increasing the mobility and
stability of the froth (Craig, 2004; Craig et al., 1993; Manono et al.,
2019, 2017; Muzenda et al., 2011) The presence of ions in the froth
impacts the liquid surface tension and inhibits bubble coalescence,
resulting in smaller and more stable bubbles and thus creating a more
stable froth (Quinn et al., 2007). Another factor that contributes to an
5
Minerals Engineering 209 (2024) 108637
increase in solids recoveries is the compression of the electrical double
layer caused by ionisation, which enhances the adherence of bubbles to
particles (Farrokhpay and Zanin, 2012) or more particles being trapped
in the plateau borders due to ions slowing inter-bubble drainage
(Manono et al., 2013(Manono et al., 2013). Recent studies proved that
increases in the ionic strength of process water as well as specific ions
increase bubble-particle attachment, more fundamental studies in the
form of zeta potential measurements, microflotation and collector
adsorption corroborated the theory that certain ions lead to the
compression of the electrical double layer, thus enhancing bubble-
particle attachment, A further possible reason for the increase in solids
and water recoveries could be that coagulants caused particles to adhere
to each other by their respective surface charges while flocculants
adhere fine particles to form larger particles (October et al., 2019, 2020,
2001). When these dewatering reagents are added to the system, it can
be expected that the size of the agglomerated particles would increase,
and the quantity of smaller sized agglomerates and individual particles
M.S. Manono et al.
Fig. 3. The Relationship between Water Recoveries and Flotation Time in Unique Plant Water with Residual Dewatering Reagents.
Fig. 4. Final Copper Grade and Recoveries in Unique Plant Water with Residual Dewatering Reagents.
would be less. Particle size is a key factor in the performance of a
flotation system, thus making it essential to have the optimal size of
particles that is not too fine or coarse (Feng and Aldrich, 1999; Norori-
McCormac et al., 2017). However, all of these possible mechanisms are
subjects of future investigations.
The specific grind size of 80 % passing 75 µm, chosen for this study,
contains a significant portion of fine particles. Fine particles have slow
recovery rates due to decreased particle-bubble collisions and have large
surface areas, which can lead to excessive adsorption of reagents and
higher oxidation of mineral surfaces (Feng and Aldrich, 1999; Lange
et al., 1997). When dewatering reagents were added to the system, they
could have interacted with the fine particles primarily due to their large
surface area resulting in aggregates, there is evidence in the literature
that dewatering aids facilitated the formation of larger aggregates from
fine particles and as a result flocculation is being pursued as a pre-
condition step for fine particle flotation and promising results have
6
Minerals Engineering 209 (2024) 108637
been reported in the literature. These aggregates which form as a result
of the influence of dewatering aids are said to result in more bubble-
particle collisions and a faster recovery rate due to their larger particle
mass (Lange et al., 1997).
3.2. Copper and nickel recoveries and grades
Fig. 4 shows cumulative copper grades and recoveries whilst Fig. 4
shows copper recoveries vs time.
Fig. 4 shows that when dewatering reagents are present in the unique
plant water, there is an increase in the recoveries of the copper bearing
minerals, the increase in copper recovery was in line with the solids
recovery in the order F > C > D > N. Having residual concentrations of
the flocculant in the process water resulted in the highest copper re­
coveries, this was followed by the coagulant in process water whilst the
depressant resulted in lower copper recoveries, however still better than
M.S. Manono et al.
Fig. 5. The Relationship between Copper Recoveries and Flotation Time in Unique Plant Water with Residual Dewatering Reagents.
Fig. 6. Final Nickel Grade and Recoveries in Unique Plant Water with Residual Dewatering Reagents.
in the absence of the coagulant, flocculant and depressant. This result is
in agreement with the proposal that bubble-particle attachment was
enhanced in process water containing residual dewatering aids.
The final copper grade was impacted significantly by the presence of
residual dewatering reagents in process water, in that the grade had an
inverse relationship with the solids recoveries. The presence of the
flocculant in process water resulted in the lowest copper grade
compared to all the dewatering aids added to the process water used
whilst process water without any of the dewatering aids had the highest
copper grade. The cumulative copper grade was shown to be in the order
F < C < D < N. Experimental conditions which resulted in the highest
solids recoveries gave rise to the lowest copper grades. This phenome­
non is expected and is in agreement other findings in the literature
which showed that higher solids recoveries resulting from both increases
in bubble-particle attachment and excessive froth stabilisation resulted
in increased gangue recoveries to the concentrate thus diluting the
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Minerals Engineering 209 (2024) 108637
quality of the concentrate collected from the froth (Corin et al., 2011;
Corin and Wiese, 2014; Manono et al., 2018b; Manono et al., 2012).
Fig. 5 shows that most of the copper was recovered in the first 2 min
of the process for all the tested conditions. The presence of residual
dewatering aids had a notable effect on copper recovery, leading to
higher copper recoveries in the process per unit time. It can also be noted
that the rate of flotation was higher in the presence of dewatering aids
compared to the baseline condition. The flocculant resulted in higher
copper flotation rates, followed by the coagulant whilst process water
with no dewatering aids resulted in the lowest rate of flotation. It can be
said that the rate of flotation was in the order F > C > D > N.
Fig. 6 shows the cumulative nickel grades and recoveries whilst
Fig. 7 shows nickel recoveries as a function of time for all tested
condition.
When residual dewatering aids were present in the unique plant
water, it can be seen that there was an increase in the recoveries of the
M.S. Manono et al. Minerals Engineering 209 (2024) 108637

Fig. 7. The Relationship between Copper Recoveries and Flotation Time in Unique Plant Water with Residual Dewatering Reagents.

Fig. 8. Turbidity vs Flotation Time.

nickel bearing mineral which is in line with the solid recoveries in the
order F > C > D > N. As for the concentrate grade with respect to nickel,
the final nickel grades had an inverse relationship with the recovery of
the nickel bearing mineral, with increasing solids and nickel recoveries,
the nickel grades decreased in a similar pattern to the copper grades,
these findings are also in agreement with previous studies (Corin et al.,
2011; Farrokhpay and Zanin, 2012; Manono et al., 2012). The decrease
in the cumulative nickel grade was in the order F < C < D < N, that is,
lower nickel grades were observed in process water containing residual
concentrations of the flocculant compared to process water containing
residual concentrations of the coagulant and depressant whilst the
highest nickel grades were seen in process water containing none of the
dewatering aids.
Fig. 7 shows that most of the recovery of the nickel bearing minerals
occurred in the first 2 min, particularly for the condition where a floc­
culant is added into the system. The coagulant and flocculant containing
conditions had the highest nickel recovery values per min while having
no reagents in process water resulted in the lowest nickel recoveries per
min. Generally, it can be seen that the addition of dewatering reagents
resulted in higher nickel flotation rates compared to the baseline con­
dition which had none of the dewatering reagents.
The trends seen in the cumulative copper and nickel recoveries and
grades shown in Fig. 4 and Fig. 6, indicate that most of the copper had
been recovered and in the order 62–74 % while nickel recoveries were in
the order 23–34 % which is substantially lower than the copper re­
coveries. This is attributed to the rates at which the minerals associated
with these metals float. It is widely acknowledged that chalcopyrite,
which is a copper-bearing sulfide mineral, has a fast rate of flotation,

8
M.S. Manono et al.
Fig. 9. Turbidity Rate of the Tailings Post Flotation.
Fig. 10. Residual SIBX Concentration in Tailings Recovered Water Post Flotation.
while pentlandite, a primary carrier of nickel in sulfide Cu-Ni-PGM ores,
floats relatively slowly compared to other sulfide minerals in Cu-Ni-PGM
ores (Becker et al., 2009; Corin et al., 2011). The decrease in grade can
be associated with a significant portion of the increased solids recovered
being that of gangue minerals as can be seen from the ore mineralogy
shown in Table 2 that a significant composition of this ore was that of
gangue minerals whilst the base metal sulfide (BMS) content was only at
0.2 wt% (i.e. only ~ 200 g BMS per kg of ore). It is known that gangue
recovery is increased through entrainment which results from an in­
crease in froth stabilisation as evidenced by the significant rise in water
recoveries shown in Fig. 1 (Farrokhpay and Zanin, 2012; Manono et al.,
2012). In this study, this is confirmed by higher water recoveries ob­
tained in process water containing residual dewatering aids and it was
therefore expected that the increase in water recoveries seen from the
presence of residual dewatering aids in process water would have
negative effects on mineral grades.
It is also suggested that the presence of residual dewatering aids in
process water resulted in a flocculation-flotation system that ensured
that fine particles formed aggregates and agglomerates that enhance
bubble-particle attachment over and beyond the entrainment of fine
9
Minerals Engineering 209 (2024) 108637
particles (Ahmadi et al., 2014; Collins and Jameson, 1976; Ding and
Laskowski, 2007; Forbes, 2011; Leistner et al., 2017; Wang, 2016).
Studies in the literature on fine particle flotation, employing flocculation
as a pre-condition step prior to flotation, have shown that flocculation
enhances floatability and recovery of fine particle through an estab­
lished mechanism by which natural and chemically aided coagulation-
flocculation agglomerates fine particles, thereby resulting in reason­
ably larger particle sizes ameanable for bubble-particle attachment and
floatability (Aruna and Shende, 2006; Chen et al., 2017; Ding and Las­
kowski, 2007; Franks et al., 2022; Smith and Miettinen, 2006). Also,
according to Lange et al. (1997), finer particles have a larger surface
area and therefore are more likely to interact with the flocculant and
coagulant resulting in larger aggregates that are better suited to particle-
bubble attachment which is the primary driver for particles that report
to the concentrate (Lange et al., 1997).
3.3. Tailings settling post flotation
Sedimentation tests were done on the tailings stream after batch
flotation. Though the focus of this study was on the influence of
M.S. Manono et al.
dewatering aids in process water on the recovery of valuable minerals to
the concentrate, consideration was also given to the sedimentation of
the tailings post-flotation. Generally, tailings arising from flotation with
process water containing residual concentrations of the coagulant and
flocculant resulted in slightly lower turbidity rate, meaning better
settling was achieved compared to tailings from flotation in process
water without residual concentrations of the coagulant and flocculant.
The difference in tailings settling behaviour can be attributed to the
flocculant and coagulant primarily interacting with the significant
number of finer particles present in the system owing to the fine grind
size.
Fig. 8 and Fig. 9 depict the results from the settling tests. In Fig. 8, the
relationship between tailings’ turbidity post-flotation and time is given
whilst Fig. 9 shows the total average turbidity rate for all the conditions
tested. It can be seen that there is little influence on the settling of the
tails as the dewatering aids were added into the unique plant water
compared to the baseline condition where no dewatering aid was pre­
sent in the process water.
Fig. 8 shows that there is one condition clearly distinct from the
others and that is D, where a residual depressant was present in process
water. The tailings slurry from flotation in process water with residual
CMC concentration took longer to settle than the other conditions as
they all settled faster, following a similar pattern and different to con­
dition D.
According to Fig. 9, the baseline condition with no residual dew­
atering aids in the process water resulted in a turbidity of − 180 NTU/
min. Tailing slurries after flotation with process water containing the
coagulant and flocculant resulted in lower turbidity rates of − 148 NTU/
min and − 162 NTU/min respectively whilst tailings from flotation with
process water consisting of residual depressant concentrations resulted
in the highest turbidity of − 202 NTU/min. This means that settling of
the tailings post flotation was in the order D > N > C = F.
If a closer consideration is given to the solids recovery to the
concentrate shown in Fig. 1, it can be inferred that the rejection of solids
to the tailings was highest where no dewatering aids were in the unique
plant water since this condition shows the lowest solids recoveries to the
concentrate. The value of the solids in the tails under the flotation
condition with no dewatering aids in process water was 856.85 g while
the lowest solids reporting to the tailings from flotation in process water
containing residual concentrations of the flocculant (F) was 749.93 g.
This indicates a significant difference in the rejection of mineral parti­
cles to the tailings for the baseline condition versus the condition with a
flocculant in process water. There is a possibility that higher residual
concentrations of dewatering reagents in process water would be
required to see a bigger impact on the settling of the tailings and should
be a subject of future research.
3.4. Residual SIBX in tailings filtrate post flotation
Fig. 10 depicts the results from the adsorption studies which allowed
for the determination of residual collector analysis on the tailings
filtrate, namely residual concentrations of SIBX. It can be seen that there
is no impact on the residual collector concentration as the dewatering
agents are added to the system.
The primary impact of dewatering agents is to cause the agglomer­
ation of fine particles into larger particles. There is an inverse rela­
tionship that exists between particle size and surface area. It is expected
that with a decrease in surface area there would be an impact on the
amount of the collector adsorbed on the mineral surface. Considering
the baseline condition (None) where no dewatering agents were present
in process water, the residual concentration of SIBX post flotation is
0.36 mg/L, when considering the error, the results indicate no obvious
impact on the adsorption of the collector as all the conditions consisting
of the dewatering reagents are well within 0.35–0.40 mg/L.
A recent study considering the adsorption of the collector in various
process waters for similar ores showed significant effects on the
10
Minerals Engineering 209 (2024) 108637
adsorption of the collector with varying degree of deterioration on the
process water quality, however this did not necessarily result in signif­
icant implications on flotation performance (Manenzhe et al., 2023).
Finer particles with larger surface area are expected to consume most
of the collector that is present in the system as they have a larger surface
area and higher specific free energy (Trahar, 1981). When dewatering
reagents are added to the process water, the quantity of fine particles
decreases, thus impacting the adsorption and causing more interaction
between the collector and coarser particles. Coarser particles would
require longer to achieve their critical hydrophobicity, thus possibly
impacting the recovery of the solids (McFadzean et al., 2012).
Since the recovery of copper and nickel was not hugely affected, it
can be assumed that the collector adsorption was not impacted. This
could be due to the dosage levels of the dewatering reagents used in this
study not being high enough to be able to reduce the surface area to such
an extent that collector adsorption would be impacted. If adsorption was
impacted, then recoveries would have been significantly impacted.
Additionally, Trahar (1981) indicated that tests done to consider the
relationship between the surface area and adsorption were not neces­
sarily proven as the methodology of testing surface area techniques
using gas adsorption was subject to differences in specific free energy.
This would lead to vastly different results.
4. Conclusions
When dewatering aids were added to the unique process water, all
conditions relative to the baseline condition resulted in the following
outcomes:
• Water and solids recoveries increased. Process water containing re­
sidual flocculant concentrations resulted in the most increase in
water and solids recoveries.
• Copper recoveries increased and were highest in process water
containing the residual flocculant.
• Copper grades decreased and were at their lowest in process water
containing the residual flocculant.
• Nickel recoveries increased and were the highest in process water
containing the residual flocculant.
• Nickel grade decreased and were at their lowest in process water
containing the residual flocculant.
• The turbidity rate of the tailings decreased slightly, implying that the
settling of the tailings improved slightly, particularly where flotation
was conducted in process water containing residual concentration of
the coagulant and flocculant.
• The adsorption analysis indicated that the adsorption of the collector
onto valuable minerals was unaffected by the presence of residual
dewatering aids in process water and remained fairly within
0.36–0.41 mg/L across the tested conditions.
These outcomes were achieved due to the primary role that floccu­
lants and coagulants play as chemicals that aid the agglomeration of
small particles in coagulation-flocculation-sedimentation processes. It
can be deduced from the results that the introduction of dewatering aids
into the process, mimicking the recycling of tailings water from dew­
atering unit operations such as thickeners into milling and flotation, may
be detrimental to flotation performance given the negative influence on
the valuable mineral grades, however these could be viewed beneficial
for a recoveries driven concentrator as valuable mineral recoveries
showed a trend of an increase.
The primary effect of having residual flocculants and coagulants in
process water during flotation was the introduction of more gangue to
the concentrate which decreased the grades of the concentrate. Findings
of this work could also benefit studies considering flocculation with
dewatering aids as a pre-conditioning step for fine particle flotation.
M.S. Manono et al.
Funding
This study benefited from funding received from the National
Research Foundation (Grant no. 118062 and 138294). Any opinions,
findings and conclusions or recommendations expressed in this material
are that of the authors and the NRF does not accept any liability in this
regard.
CRediT authorship contribution statement
Malibongwe S. Manono: Conceptualization, Data curation, Formal
analysis, Funding acquisition, Investigation, Methodology, Project
administration, Resources, Software, Supervision, Writing – original
draft, Writing – review & editing. Saahil F. Khan: Data curation, Formal
analysis, Investigation, Methodology, Writing – original draft. Lisa L.
October: Conceptualization, Data curation, Formal analysis, Investiga­
tion, Methodology, Project administration, Resources, Supervision,
Writing – review & editing. Kirsten C. Corin: Investigation, Method­
ology, Project administration, Resources, Supervision, Writing – review
& editing.
Declaration of competing interest
The authors declare the following financial interests/personal re­
lationships which may be considered as potential competing interests:
Malibongwe S. Manono reports financial support was provided by the
National Research Foundation (NRF) in South Africa.
Data availability
Data will be made available on request.
Acknowledgments
The authors would like to acknowledge Mpho Ramonotsi who
assisted in the acquisition of the ore and reagents used in this study.
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